The present invention relates to a process for the preparation of manganese complexes of salen compounds, to the compounds prepared according to that process, and to the use thereof in washing and cleaning solutions.
Manganese complexes of salen compounds are known, for example, from EP-A-902 083 and EP-A-955 289. They are usually prepared from the appropriate salen ligands by reaction with a manganese salt in ethanolic solution in the presence of air as oxidizing agent. The ligands themselves are obtained, for example, by reacting the appropriate di- or tri-amines with the appropriate o-hydroxyaldehydes in methanolic or ethanolic solution and crystallising out the ligands. Since, however, on an industrial scale working in methanol or ethanol at elevated temperature in the presence of air necessitates complex safety measures, the need existed for an improved method of synthesis.
It has now been found, surprisingly, that the reaction of the ligand with the manganese salt can advantageously be carried out in dimethylformamide (DMF) as solvent, and at the same time it is possible to operate at a temperature sufficiently far below the flash point of the solvent that even in the presence of air there are no safety problems. The preparation of the ligand can be carried out, for example, in water or, preferably, likewise in DMF. Surprisingly, it is even possible to carry out the synthesis of the ligand and the preparation of the manganese complex in DMF as a xe2x80x9cone-pot reactionxe2x80x9d, that is to say without isolation and purification of the ligand.
The present invention accordingly relates to a process for the preparation of manganese complexes of salen compounds of formula 
in which formulae
A is an anion;
n, m and p are each independently of the others 0, 1, 2 or 3,
R, R1 and R1xe2x80x2 are each independently of the others cyano; halogen; OR4 or COOR4, wherein R4 is hydrogen or linear or branched C1-C4alkyl; nitro; linear or branched C1-C8alkyl; linear or branched partially fluorinated or perfluorinated C1-C8alkyl; NR5R6, wherein R5 and R6 are identical or different and are each independently of the other hydrogen or linear or branched C1-C12alkyl; or linear or branched C1-C8alkyl-R7, wherein R7 is a radical NH2, OR4, COOR4 or NR5R6 as defined above; or xe2x80x94CH2xe2x80x94N⊕R4R6R7 or xe2x80x94N⊕R4R5R6, wherein R4, R5 and R6 are as defined above,
R2 and R3 are each independently of the other hydrogen, linear or branched C1-C4alkyl or unsubstituted aryl or aryl that is substituted by cyano; by halogen; by OR4 or COOR4, wherein R4 is hydrogen or linear or branched C1-C4alkyl; by nitro; by linear or branched C1-C8alkyl; by NHR5 or NR5R6, wherein R5 and R6 are identical or different and are each hydrogen or linear or branched C1-C12alkyl or wherein R5 and R6 together with the nitrogen atom linking them form a 5-, 6- or 7-membered ring that may contain further hetero atoms; or by linear or branched C1-C8alkyl-R7, wherein R7 is a radical NH2, OR4, COOR4 or NR5R6 as defined above; or by xe2x80x94N⊕R4R5R6, wherein R4, R5 and R6 are as defined above,
R8 radicals are each independently of the others hydrogen or linear or branched C1-C4alkyl,
Y is a linear or branched alkylene radical of formula xe2x80x94[C(R4)2]rxe2x80x94, wherein r is an integer from 1 to 8 and the R4 radicals are each independently of any other(s) as defined above; xe2x80x94CXxe2x95x90CXxe2x80x94, wherein X is cyano, linear or branched C1-C8alkyl or di(linear or branched C1-C8alkyl)amino; xe2x80x94(CH2)qxe2x80x94NR4xe2x80x94(CH2)qxe2x80x94, wherein R4 is as defined above and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene radical of formula: 
wherein R9 is hydrogen, SO3H, CH2OH or CH2NH2,
wherein in formula (1) the phenyl rings may together carry no more than three tert-butyl substituents, and wherein, when Y is 2-hydroxypropylene and m and n are each 0, R2 and R3 may not both be H, and wherein when Y is ethylene or o-phenylene and m and n are each 0 and MnO is used as the manganese compound, R2 and R3 may not both be H,
which process comprises reacting a ligand of formula 
wherein R, R1, R1xe2x80x2, R2, R3, R4, R5, R6, R7, R8, R9, Y, A, n, m and p are as defined for formulae (1), (2) and (3),
with a manganese compound in dimethylformamide as solvent.
In the compounds of formula (1) or (3) in which n, m or p is 2 or 3, the radicals R, R1 and R1xe2x80x2 have identical or different meanings. The same applies to compounds of formula (2) in respect of the R8 radicals.
When Y is a 1,2-cyclohexylene radical, that radical may be in either of its stereoisomeric cis/trans forms.
Preferably, Y is a radical of formula xe2x80x94(CH2)rxe2x80x94 wherein r is an integer from 1 to 8, or a radical of formula xe2x80x94C(R5)2xe2x80x94(CH2)pxe2x80x94C(R5)2xe2x80x94 wherein p is a number from 0 to 6 and R5 is hydrogen or C1-C4alkyl.
In especially preferred compounds of formulae (1) and (2), Y is a radical of formula xe2x80x94(CH2)rxe2x80x94 wherein r is an integer from 1 to 4, or a radical of formula xe2x80x94(CR5)2xe2x80x94(CR5)2xe2x80x94 wherein the R5 radicals are each independently of the others hydrogen or methyl.
Halogen is preferably chlorine, bromine or fluorine, chlorine being especially preferred.
When R, R1 or R1xe2x80x2 is di(C1-C12alkyl)amino, the alkyl group may be straight-chain or branched. Preferably it contains from 1 to 8, especially from 1 to 4, and more especially 1 or 2, carbon atoms.
Preferably, the radicals R, R1 and R1xe2x80x2 are hydrogen, nitro, OR4, COOR4 or N(R4)2, wherein R4 is hydrogen or C1-C4alkyl, especially methyl or ethyl.
The radicals R2 and R3 are especially hydrogen, methyl, ethyl or unsubstituted phenyl.
Aryl is, for example, naphthyl or especially phenyl.
When R5 and R6 together with the nitrogen atom linking them is a 5-, 6- or 7-membered ring, that ring is especially a pyrrolidine, piperidine, morpholine or piperazine ring. The piperazine ring may be substituted, for example by alkyl, at the nitrogen atom that is not bonded to the phenyl radical.
Suitable anions include, for example, halide, for example chloride, perchlorate, sulfate, nitrate, hydroxide, BF4xe2x88x92, PF6xe2x88x92, carboxylate, acetate, tosylate and triflate. Of those, preference is given to chloride, acetate and carboxylate.
The ligands of formulae (4), (5) and (6) are known or can be prepared in a manner known per se.
In the process according to the invention, the reaction of those ligands with a manganese compound is carried out in DMF at a temperature of from approximately 10xc2x0 C. to the boiling point of DMF, but preferably at a temperature of from 20 to 70xc2x0 C., especially from 20 to 40xc2x0 C.
The manganese compounds used are especially manganese(II) salts, especially manganese(II) chloride, sulfate or acetate.
Preferably, the manganese compound is added in slight excess, especially an excess of from 0.5 to 3%.
During the reaction, preferably air, as oxidizing agent, is passed through the reaction mixture, but it is also possible to use other oxidizing agents.
After the reaction, the manganese complex is isolated in a manner known per se, for example by crystallising it out by the addition of sodium chloride and then distilling off the DMF at elevated temperature in vacuo, suspending the residue in water and filtering.
In an especially preferred embodiment of the process according to the invention, the ligands used have not been formed and isolated beforehand but instead the synthesis of the ligand and the reaction to form the manganese complex are carried out in DMF as a so-called one-pot reaction.
The present invention accordingly relates also to a process for the preparation of manganese complexes of the above formulae (1), (2) and (3) which comprises, in DMF as solvent, reacting a diamine of formula
H2Nxe2x80x94Yxe2x80x94NH2xe2x80x83xe2x80x83(7)
with an o-hydroxybenzaldehyde of formula 
or reacting the compound of formula
N(xe2x80x94CH2xe2x80x94CH2xe2x80x94NH2)3xe2x80x83xe2x80x83(10)
with an o-hydroxybenzaldehyde of formula (8), in which formulae R, R2, R8 and n are as defined for formulae (1) and (2), and then, without intermediate isolation, reacting the resulting salen compound with a manganese compound to form a manganese complex of formula (1), (2) or (3).
The first reaction is carried out at approximately from 10 to 40xc2x0 C., preferably at room temperature, and di- or tri-amine and aldehyde are preferably used approximately in a molar ratio of 1:2 or 1:3, respectively.
The reaction conditions for the second step correspond to the conditions described above for the synthesis of the manganese complexes from ligand and manganese compound.
The manganese complexes are in that manner obtained with a good level of purity and a high yield according to a very simple process. They are used especially as catalysts that enhance the action of peroxy compounds in washing, cleaning and disinfecting procedures.
The following Examples serve to illustrate the invention but do not limit the invention thereto. Unless specified otherwise, parts and percentages relate to weight.